CN107814730A - A kind of preparation method of the line style pectination epoxy polyamine compounds of the tertiary amine groups containing side - Google Patents
A kind of preparation method of the line style pectination epoxy polyamine compounds of the tertiary amine groups containing side Download PDFInfo
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- CN107814730A CN107814730A CN201710796724.5A CN201710796724A CN107814730A CN 107814730 A CN107814730 A CN 107814730A CN 201710796724 A CN201710796724 A CN 201710796724A CN 107814730 A CN107814730 A CN 107814730A
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- tertiary amine
- amine groups
- line style
- polyamine compounds
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 40
- 229920000768 polyamine Polymers 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 125000001302 tertiary amino group Chemical group 0.000 title abstract 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 56
- -1 aliphatic diamine compound Chemical class 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 5
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 5
- 150000003512 tertiary amines Chemical group 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 21
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 150000002118 epoxides Chemical group 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical class CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 125000003368 amide group Chemical group 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical class CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 3
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical class C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 3
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 claims description 3
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical class CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 2
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005997 bromomethyl group Chemical group 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 claims 1
- MTVUDFBYBPMGMR-UHFFFAOYSA-N 1-ethyl-2-propylhydrazine Chemical compound CCCNNCC MTVUDFBYBPMGMR-UHFFFAOYSA-N 0.000 claims 1
- VTEBEHXYQSENAU-UHFFFAOYSA-N C(C1CO1)C(C(C(O)CC1CO1)O)O.C(COCCO)O Chemical compound C(C1CO1)C(C(C(O)CC1CO1)O)O.C(COCCO)O VTEBEHXYQSENAU-UHFFFAOYSA-N 0.000 claims 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims 1
- JILXUIANNUALRZ-UHFFFAOYSA-N n',n'-diethylbutane-1,4-diamine Chemical compound CCN(CC)CCCCN JILXUIANNUALRZ-UHFFFAOYSA-N 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 150000003335 secondary amines Chemical group 0.000 description 8
- 150000003141 primary amines Chemical class 0.000 description 7
- 229920006317 cationic polymer Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/502—Polyalkylene polyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of preparation method of the line style pectination epoxy polyamine compounds of tertiary amine groups containing side, comprise the following steps：Using 2-glycidyl ethers compound and the aliphatic diamine compound containing tertiary amine groups as raw material, it is 1.1~2.0 to control the mol ratio of the aliphatic diamine compound containing tertiary amine groups and 2-glycidyl ethers compound：1.0,1~24h is reacted in 30~120 DEG C under nitrogen protection, is prepared by the ammonolysis ring-opening reaction of epoxide group.The raw material of the preparation method is conveniently easy to get, synthesis condition is gentle, synthesis technique is simple, is advantageous to industrialization production and the business promotion application of the line style pectination epoxy polyamine compounds of the tertiary amine groups containing side.
Description
Technical field
The present invention relates to the synthesis technical field of organic compound, in particular it relates to a kind of line style comb of tertiary amine groups containing side
The preparation method of shape epoxy polyamine compounds.
Background technology
Epoxide refers to ether and its derivative containing three-membered ring, because three-membered ring structures have larger ring
Power so that the chemical property of epoxide is very active.Under the catalytic action of acid or alkali, it is easily opened with nucleopilic reagent
Ring reacts, and obtains many important chemical intermediates.Thus, epoxide is considered as most important in organic synthesis and application
One of most wide raw material.Fat amine compound has stronger alkalescence, in the case where being acted on without extra catalyst, fat primary amine and secondary
Amine groups just can carry out ammonolysis epoxy ring opening reaction with epoxy radicals at room temperature.E.g., including diethylenetriamine and triethylene four
Numerous amine compounds of amine are exactly one of Common Curing Agents of epoxy resin [progress of hardener for epoxy resin
[J] modern coatings and application, 2007,10 (4)：37-40.].
2-glycidyl ethers compound contains two active epoxide groups, by with two of both ends containing primary amine or secondary amine
Degree of functionality amine compound reacts, and controls the mol ratio of the two, can obtain the epoxy polyamine compounds of linear structure.It is elected
Reacted with two degree of functionality amine compounds of the both ends containing secondary amine and 2-glycidyl ethers compound, then can obtain main chain and contain uncle
Amido, the phenol epoxy polyamine compounds that end group is secondary amine.However, when using this kind of phenol epoxy polyamine compounds as raw material system
During standby cationic polymer, because the tertiary amine group steric hindrance on main chain is larger so that subsequently carry out cationization to it and change
It is more difficult during property.When gained cationic polymer is dispersed in water, because tertiary amine group " inlaying " is on main chain, molecule
The winding of chain and package action easily get up the tertiary amine salt groups " parcel " of partial hydrophilicity, do not have hydrophilic interaction, and then
Influence the water dispersion effect and stability [the novel cation UV Curable Cationic Electrodeposition Coatings of side base ammonium salt-containing of cationic polymer
[J] Journal of Chemical Industry and Engineering, 2015,66 (11):4696-4702.].Therefore, the present invention intends providing a kind of line style comb of tertiary amine groups containing side
Shape epoxy polyamine compounds, tertiary amine group on its side chain are smaller due to steric hindrance, it can be ensured that tertiary amine group is in cation
Good chemical reactivity when changing modified；Meanwhile after the tertiary amine groups on side chain are cationized, due to the winding of strand
It is smaller with package action, the cation prepared using the line style pectination epoxy polyamine compounds of the tertiary amine groups containing side as raw material can be assigned
The more preferable hydrophily of polymer, and then preferably water dispersion effect.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of line style pectination epoxy polyamine compounds of tertiary amine groups containing side,
Tertiary amine group on its side chain is smaller due to steric hindrance, it can be ensured that the tertiary amine group chemistry good in cation modifying
Reactivity；Meanwhile after the tertiary amine groups on side chain are cationized, the winding and package action due to strand are smaller, energy
Enough impartings are preferably hydrophilic as cationic polymer prepared by raw material using the line style pectination epoxy polyamine compounds of the tertiary amine groups containing side
Property, and then preferably water dispersion effect.The invention provides a kind of line style pectination epoxy polyamines chemical combination of tertiary amine groups containing side
The preparation method of thing.
Technical scheme is as follows：
A kind of preparation method of the line style pectination epoxy polyamine compounds of tertiary amine groups containing side, comprises the following steps：With two contractings
Water glycerine ether compound and aliphatic diamine compound containing tertiary amine groups are raw material, control the aliphatic diamine containing tertiary amine groups
The mol ratio of compound and 2-glycidyl ethers compound is 1.1~2.0：1.0, react 1 in 30~120 DEG C under nitrogen protection
~24h, it is prepared by the ammonolysis ring-opening reaction of epoxide group, there is following skeleton symbol：
Wherein, R1For-O- ,-OCH2CH2O-、-OCH2CH2CH2CH2O-、-OCH2CH2CH2CH2CH2CH2O-、 -OCH2CH2OCH2CH2O-、 In any one or its combination, R2For any one in methyl and ethyl or its
Combination, m, n, a and b meet 1≤m≤10,2≤n≤4,4≤a≤45,7≤b≤51, and are positive integer.
In above-mentioned preparation method, described 2-glycidyl ethers compound is diglycidyl ether, ethylene glycol two shrinks
Glycerin ether, 1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidylether, 1,4 cyclohexane dimethanol glycidol
Ether, bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, diethylene glycol diglycidyl ether, DPG two contract
Double (the bromomethyl) -1,3- propane diols two of water glycerin ether, glycerine diglycidyl ether, neopentylglycol diglycidyl ether, 2,2-
Double (3- glycydoxies) tetramethyl disiloxanes of glycidol ether, 1,3-, polyethyleneglycol diglycidylether and
Any one in polypropylene glycol diglycidyl ether or its combination.
Preferably, described 2-glycidyl ethers compound be diglycidyl ether, ethylene glycol diglycidylether,
1,4- butanediol diglycidyl ethers, diethylene glycol diglycidyl ether, DPG diglycidyl ether, 1,3- are double
(3- glycydoxies) tetramethyl disiloxane, polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl
Any one in ether or its combination.
In above-mentioned preparation method, the aliphatic diamine compound containing tertiary amine groups is N, N- dimethyl-ethylenediamines, N,
N- diethyl ethylenediamines, 3- dimethylamine propylamines, 3- diethyl amino propylamines, 4- dimethylaminobutylamines and 4- diethylamino fourths
Any one in amine or its combination.
Preferably, the aliphatic diamine compound containing tertiary amine groups is N, N- dimethyl-ethylenediamines, 3- dimethylamine
Any one in base propylamine and 4- dimethylaminobutylamines or its combination.
In above-mentioned preparation method, the aliphatic diamine compound and 2-glycidyl ethers compound containing tertiary amine groups
Mol ratio be 1.1~2.0：1.0.
Preferably, mole of the aliphatic diamine compound and 2-glycidyl ethers compound containing tertiary amine groups
Than for 1.2~2.0：1.0.
In above-mentioned preparation method, described reaction temperature is 30~120 DEG C.
Preferably, described reaction temperature is 60~100 DEG C.
In above-mentioned preparation method, the described reaction time is 1~24h.
Preferably, the described reaction time is 2~8h.
In the present invention, tertiary amine groups are contained in described aliphatic diamine compound one end containing tertiary amine groups, and the other end contains primary
Amido, amido and the activity order of epoxide group reaction are primary amine ＞ secondary amine ＞ tertiary amines.The chemical reaction of primary amine and epoxide group
Skeleton symbol is as shown in figure 1,1mol primary amine groups react to obtain 1mol secondary amines (Fig. 1 (1)) with 1mol epoxide groups, and then, 1mol is secondary
Amido reacts to obtain 1mol tertiary amine groups (Fig. 1 (2)) again with 1mol epoxide groups.Therefore, the aliphatic diamine chemical combination containing tertiary amine groups
Thing can be regarded as the compound of two degrees of functionality when being reacted with 2-glycidyl ethers compound, be represented with A-A, A represents primary amine
A hydrogen atom on base.And 2-glycidyl ethers compound contains two epoxide groups, the chemical combination of two degrees of functionality is similarly
Thing, represented with B-B, B represents epoxide group.When the m+1mol aliphatic diamine compound containing tertiary amine groups is shunk with m mol bis-
When glycerine ether compound reacts, their reaction skeleton symbol is as shown in Figure 2.
By the mol ratio (m+ for controlling aliphatic diamine compound and 2-glycidyl ethers compound containing tertiary amine groups
1)/m is 1.2~2.0：1.0, it is more that the line style pectination epoxy that end group is the tertiary amine groups containing side of secondary amine, side base containing tertiary amine groups can be obtained
Amines.
The present invention is advantageous in that：
1st, the line style pectination epoxy polyamine compounds of the tertiary amine groups of the present invention containing side, the tertiary amine groups in its side base are compared
Tertiary amine groups steric hindrance on main chain substantially reduces, it can be ensured that the tertiary amine group chemism good in subsequent reactions.
2nd, the line style pectination epoxy polyamine compounds of the tertiary amine groups of the present invention containing side, its end group is containing active higher
Secondary amine, it can be chemically reacted with groups such as epoxy radicals, NCO and carboxyls to prepare cationic polymer, due to
The winding of strand offside tertiary amine groups and package action are smaller, can assign the gained more preferable hydrophily of cationic polymer, enter
And reach more preferable water dispersion effect.
3rd, the raw material of preparation method of the present invention is conveniently easy to get, synthesis condition is gentle, synthesis technique is simple, is advantageous to contain
The industrialization production of the line style pectination epoxy polyamine compounds of side tertiary amine groups and business promotion application.
Brief description of the drawings
Fig. 1：The chemical equation of primary amine and epoxide group；
Fig. 2：The reaction of aliphatic diamine compound (A-A) and 2-glycidyl ethers compound (B-B) containing tertiary amine groups
Skeleton symbol.
Embodiment
The preparation method of the line style pectination epoxy polyamine compounds of a kind of tertiary amine groups containing side, with 2-glycidyl ethers chemical combination
Thing and aliphatic diamine compound containing tertiary amine groups are raw material, control the aliphatic diamine compound containing tertiary amine groups and two shrink it is sweet
The mol ratio of oily ether compound is 1.1~2.0：1.0,1~24h is reacted in 30~120 DEG C under nitrogen protection, passes through epoxy
The ammonolysis ring-opening reaction of group is made.
Embodiment 1：
117.53g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 2 for N, N- dimethyl-ethylenediamine and 86.76g diglycidyl ethers:1, m=1, n=2), it is passed through nitrogen and puts
Change three times, be warming up to 60 DEG C of reaction 8.0h under agitation, obtain the line style pectination epoxy polyamine compounds 1 of the tertiary amine groups containing side.
Embodiment 2：
85.22g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.1 for N, N- diethyl ethylenediamine and 116.13g ethylene glycol diglycidylethers:1, m=10, n=2),
It is passed through nitrogen displacement three times, is warming up to 30 DEG C of reaction 24.0h under agitation, obtains the line style pectination epoxy polyamines of the tertiary amine groups containing side
Compound 2.
Embodiment 3：
40.87g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.2 for 3- dimethylamine propylamines and 113.47g bisphenol A diglycidyl ethers:1, m=5, n=3), it is passed through
Nitrogen displacement three times, is warming up to 100 DEG C of reaction 2.0h, obtains the line style pectination epoxy polyamines chemical combination of the tertiary amine groups containing side under agitation
Thing 3.
Embodiment 4：
65.11g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.5 for 3- diethyl amino propylamines and 72.67g diethylene glycol diglycidyl ethers:1, m=2, n=
3), it is passed through nitrogen displacement three times, is warming up to 120 DEG C of reaction 1.0h under agitation, obtains the line style pectination epoxy of the tertiary amine groups containing side
Polyamine compounds 4.
Embodiment 5：
48.42g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both rubs for 4- dimethylaminobutylamines and double (3- glycydoxies) tetramethyl disiloxanes of 120.87g 1,3-
You are than being 1.25:1, m=4, n=4), it is passed through nitrogen displacement three times, is warming up to 80 DEG C of reaction 6.0h under agitation, obtains containing side
The line style pectination epoxy polyamine compounds 5 of tertiary amine groups.
Embodiment 6：
63.95g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.33 for 4- diethylaminos butylamine and 72.09g neopentylglycol diglycidyl ethers:1, m=4, n=4),
It is passed through nitrogen displacement three times, is warming up to 80 DEG C of reaction 8.0h under agitation, obtains the line style pectination epoxy polyamines of the tertiary amine groups containing side
Compound 6.
Embodiment 7：
32.32g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.1 for N, N- dimethyl-ethylenediamine and 102.0g polyethyleneglycol diglycidylethers:1, m=10, n=2, a
=4), it is passed through nitrogen displacement three times, is warming up to 80 DEG C of reaction 6.0h under agitation, obtains the line style pectination epoxy of the tertiary amine groups containing side
Polyamine compounds 7.
Embodiment 8：
20.44g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 2.0 for 3- dimethylamine propylamines and 211.0g polyethyleneglycol diglycidylethers:1, m=1, n=3, a=
45), it is passed through nitrogen displacement three times, is warming up to 80 DEG C of reaction 10.0h under agitation, obtains the line style pectination epoxy of the tertiary amine groups containing side
Polyamine compounds 8.
Embodiment 9：
43.58g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.5 for 4- dimethylaminobutylamines and 175.5g polyethyleneglycol diglycidylethers:1, m=2, n=4, a
=13), it is passed through nitrogen displacement three times, is warming up to 60 DEG C of reaction 10.0h under agitation, obtains the line style pectination ring of the tertiary amine groups containing side
Oxygen polyamine compounds 9.
Embodiment 10：
24.24g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.1 for N, N- dimethyl-ethylenediamine and 134.0g polypropylene glycol diglycidyl ethers:1, m=10, n=2, b
=7), it is passed through nitrogen displacement three times, is warming up to 80 DEG C of reaction 6.0h under agitation, obtains the line style pectination epoxy of the tertiary amine groups containing side
Polyamine compounds 10.
Embodiment 11：
11.75g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 2.0 for N, N- dimethyl-ethylenediamine and 205.87g polypropylene glycol diglycidyl ethers:1, m=1, n=2, b
=51), it is passed through nitrogen displacement three times, is warming up to 70 DEG C of reaction 8.0h under agitation, obtains the line style pectination ring of the tertiary amine groups containing side
Oxygen polyamine compounds 11.
Embodiment 12：
17.63g is separately added into the 250mL four-hole boiling flasks with thermometer, agitator, condenser pipe and nitrogen inlet
(both mol ratios are 1.5 for N, N- dimethyl-ethylenediamine and 116.0g polypropylene glycol diglycidyl ethers:1, m=2, n=2, b
=17), it is passed through nitrogen displacement three times, is warming up to 70 DEG C of reaction 8.0h under agitation, obtains the line style pectination ring of the tertiary amine groups containing side
Oxygen polyamine compounds 12.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (8)
1. the preparation method of the line style pectination epoxy polyamine compounds of a kind of tertiary amine groups containing side, it is characterised in that including following step
Suddenly：Using 2-glycidyl ethers compound and the aliphatic diamine compound containing tertiary amine groups as raw material, the fat containing tertiary amine groups is controlled
The mol ratio of fat race diamine compound and 2-glycidyl ethers compound is 1.1~2.0：1.0, under nitrogen protection in 30~
120 DEG C of 1~24h of reaction, are prepared by the ammonolysis ring-opening reaction of epoxide group, have following skeleton symbol：
Wherein, R1For-O- ,-OCH2CH2O-、-OCH2CH2CH2CH2O-、-OCH2CH2CH2CH2CH2CH2O-、 -OCH2CH2OCH2CH2O-、 In any one or its combination, R2For any one in methyl and ethyl or its
Combination, m, n, a and b meet 1≤m≤10,2≤n≤4,4≤a≤45,7≤b≤51, and are positive integer.
2. the preparation method of the line style pectination epoxy polyamine compounds of the tertiary amine groups containing side, its feature exist as claimed in claim 1
In described 2-glycidyl ethers compound is diglycidyl ether, ethylene glycol diglycidylether, BDO two contract
Water glycerin ether, 1,6 hexanediol diglycidylether, 1,4 cyclohexane dimethanol glycidol ether, bisphenol A diglycidyl ether,
Bisphenol F diglycidyl ether, diethylene glycol diglycidyl ether, DPG diglycidyl ether, glycerine two shrink sweet
Double (the bromomethyl) -1,3- propylene glycol diglycidylethers of oleyl ether, neopentylglycol diglycidyl ether, 2,2-, 1,3- are double, and (3- contracts
Water glycerin ether epoxide propyl group) in tetramethyl disiloxane, polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether
Any one or its combination.
3. the preparation method of line style pectination epoxy polyamine compounds as claimed in claim 2, it is characterised in that two described contractings
Water glycerine ether compound is diglycidyl ether, ethylene glycol diglycidylether, 1,4- butanediol diglycidyl ethers, a contracting
Double (3- glycydoxies) tetramethyls of diethylene glycol diglycidyl glycerin ether, DPG diglycidyl ether, 1,3-
Any one in disiloxane, polyethyleneglycol diglycidylether and polypropylene glycol diglycidyl ether or its combination.
4. the preparation method of line style pectination epoxy polyamine compounds as claimed in claim 1, it is characterised in that described contains uncle
The aliphatic diamine compound of amido is N, N- dimethyl-ethylenediamines, N, N- diethyl ethylenediamines, 3- dimethylamine propylamines, 3- bis-
Any one in ethylamino- propylamine, 4- dimethylaminobutylamines and 4- diethylamino butylamine or its combination.
5. the preparation method of line style pectination epoxy polyamine compounds as claimed in claim 4, it is characterised in that described contains uncle
The aliphatic diamine compound of amido is N, in N- dimethyl-ethylenediamines, 3- dimethylamine propylamines and 4- dimethylaminobutylamines
Any one or its combination.
6. the preparation method of line style pectination epoxy polyamine compounds as claimed in claim 1, it is characterised in that described contains uncle
The aliphatic diamine compound of amido and the mol ratio of 2-glycidyl ethers compound are 1.2~2.0：1.0.
7. the preparation method of line style pectination epoxy polyamine compounds as claimed in claim 1, it is characterised in that described reaction
Temperature is 60~100 DEG C.
8. the preparation method of line style pectination epoxy polyamine compounds as claimed in claim 1, it is characterised in that described reaction
Time is 2~8h.
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| CN108752577A (en) * | 2018-06-25 | 2018-11-06 | 烟台大学 | The auxiliary agent and its application method that tannin is spread in a kind of inhibition timber |
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| CN109206574A (en) * | 2018-06-25 | 2019-01-15 | 青岛海尔股份有限公司 | Glycol composition and its polyurethane rigid foam plastic of preparation |
| CN116375991A (en) * | 2023-04-14 | 2023-07-04 | 泰州市正大化工有限公司 | A hyperdispersant and its application in light-cured coatings |
| CN117820087A (en) * | 2022-09-29 | 2024-04-05 | 中国石油化工股份有限公司 | A preparation method of bisphenol A-based diglyceryl ether compounds |
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